Process for preparing 2,3-dihydro-1h,6h-1,5-benzodiazocine-2-one derivative

ABSTRACT

A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2one derivatives represented by the formula (II), comprising irradiating an organic solution of spiro(indoline-2,5&#39;&#39;isoxazoline-2) represented by the formula (I) with light   WHEREIN R1, R2 and R3 each represents a hydrogen atom or alkyl group having 1-4 carbon atoms, R4 represents a hydrogen atom, alkyl group having 1-4 carbon atoms, alkoxy group having 1-4 carbon atoms, alkoxycarbonyl group having 1-4 carbon atoms, nitro group, halogen atom or such a substituent that forms dimer bonded through methylene chain, R represents phenyl group substituted by the substituent of R4, or such a substituent that forms dimer bonded through alkyl chain or phenylene group.

United States Patent 1191 Ono et al.

[ PROCESS FOR PREPARING 2,3-DIHYDRO-1I-I, 6H-1,5-BENZODIAZOCINE-2-ONE DERIVATIVE [75] Inventors: Hisatake Ono; I-Iarumi Katsuyama,

both of Asaka, Japan [73] Assignee: Fuji Photo Film Co., Ltd., Minami Ashigara-shi, Kanagawa, Japan 22 Filed: Feb. 16, 1972 211 App]. No.: 226,742

[30] Foreign Application Priority Data Primary E.\'aminerl-loward S. Williams Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A process for preparing 2,3-dihydro-lH,6H-l,5-

1451 Apr.9, 1974 benzodiazocine-Z-one derivatives represented by the formula (ll), comprising irradiating an organic solution of spiro(indoline-2,5-isoxazoline-2) represented by the formula (I) with light wherein R R and R each represents a hydrogen atom or alkyl group having l-4 carbon atoms, R represents a hydrogen atom, alkyl group having 1-4 carbon atoms, alkoxy group having l-4 carbon atoms, alkoxycarbonyl group having l-4 carbon atoms, nitro group, halogen atom or such a substituent that forms dimer bonded through methylene chain, R represents phenyl group substituted by the substituent of R or such a substituent that forms dimer bonded through alkyl chain or phenylcne group.

15 Claims, 2 Drawing Figures PATENTEDAPR 9 I974 iazma $230 Mmu) To i i Ewzma 550 PROCESS FOR PREPARING 2,3-DlHYDRO-1H, 6H-1,S-BENZODIAZOCINE-Z-ONE DERIVATIVE Since benzodiazocine derivatives belong to a novel heterocyclic group, they are noteworthy compounds because of their pharmacological effects, photoconductivity, etc. But, so far, few processes for the synthesis thereof have been reported. This invention relates to a process for synthesizing such benzodiazocine derivatives of 2,3-dihydro-1H, 6H-l,5-benzodiazocine- 2-ones having quite a novel structure, more particularly, it relates t o a process for preparing desired 2,3- dihydro-IH, 6H-l,4-benzodiazocine-2-ones by the photoisomerization of spiro (indoline-2,5-isoxazoline- 2) compounds. According to this invention, the compounds having a spiro(indoline-2,5'-isoxazoline-2) skeleton can be easily converted to the corresponding 2,3-dihydrol H, 6H- 1 ,S-benzodiazocine-Z-one compounds by the photochemical isomerization reaction.

The reaction can be described as follows;

wherein R R and R each represents a hydrogen atom or alkyl group having l lcarbon ato msflii represents a hydrogen atom, alkyl group having 1-4 carbon atoms, alkoxy group having l-4 carbon atoms, alkoxycarbonyl group having l-4 carbon atoms, nitro group, halogen atom or such a substituent that forms a dimer bonded through a methylene chain, R represents a phenyl group substituted by the substituent of R or such a substituent that forms a dimer bonded through an alkyl chain or phenylene group.

The starting material used in the reaction of this invention was newly synthesized by us before, and the process thereof has been submitted to the Japanese Patent Office as Process for preparing compounds having a novel spiro (indoline-2,5-isoxazoline) structure. (Japanese Pat. application No. 86238/70, now Japanese Pat. Publication No. 7l0l/73, which corresponds to US. Pat. application 1858 1 8/71, German OLS 2,149,229 and French Pat. application No. 2,109,939).

Every product of this invention exhibits photoconductivity, and is utilized for making a photo-conductive material and, in addition, it is utilized as an intermediate for synthesizing compounds containing a heteroring such as a sensitizing dye, etc.

When the organic solution (e.g., cyclohexane, methanol, tetrahydrofuran, etc.) of spiro(indoline-2,5- isoxazoline-Z) was exposedto thelight of high pressure mercury lamp (Toshiba SHL-IOOUV), and the change of the ultraviolet absorption spectrum thereof was followed, the reaction of this invention was found to be the reaction accompanied by a very gu ick absorption spectrum change (the reaction was finished within 1 minute at the concentration of 10- mol/ 1) having an isosbestic point.

FIG. I is the graph on which the change of the ultraviolet absorption spectrum in the photoisomerization reaction of 5-chloro-l,3,3-trimethyl-3 -phenylspiro(ind oline-2,5'-isoxazoline-2) -to 8-chloro-2,3-dihydro2- oxo-4-phenyl-l ,6,6-trimethyll H, benzodiazocine was recorded.

T 4am as .QP PFYQQ by p n the solution of the said compound (10- mol/l) to the light for 0, 5, l0, 15, 20, 30 and 60 seconds using a Toshiba SHL- lOOUV high pressure mercury lamp.

Examples of the spiro(indoline-2,5'-isoxazoline-2) which undergoes this photochemical reaction are 1,3,- 3-trimethyl-3 '-phenylspiro( indoline-2,5 '-isoxazoline- 2), 5-chlorol ,3,3-trimethyl-3 -phenyl-spiro( indoline- 2,5 '-isoxazoline-2 l ,3 ,3-trimethyl-3 '-p-tolylspiro (indoline-2,5 -isoxazoline-2), 5 -ethoxycarbonyll ,3 ,3- trimethyl-3 -panisylspiro( indoline-2,5 -isoxazoline-2 l ,3,3-trimethyl-3 -p-chlorophenylspiro( indoline-2,5 isoxazoline-Z), 5 'nitrol ,3 ,3-trimethyl-3 phenylspiro(indoline-2,5 '-isoxazoline-2), l ,3 ,3- trimethyl-3 -m-nitrophenylspiro( indoline-2 ,5 isoxazoline-2), 3, 3 '-bis 1,3,3-trimethylspiro( indoline 2,5 -isoxazoline-Z 3 T bisfi-chloro-l ,3 ,3-trimethylspiro(indoline-2,5 isoxazoline-2)], 3,3-bis[5-ethoxycarbonyl-1,3,3- trimethylspiro(indoline-2,5-isoxazoline-2)], 3, 3-bis[5-methoxyl ,3 ,3-trimethylspiro(indoline-2,5 isoxazoline-2)],3 ,3-p-phenylenebis [1,3,3-trimethylspiro(indoline-2,5-isoxazoline-2)] and the high molecular weight compound which has the main chain of spiro(indoline-2,5-isoxazoline-2) and is described as follows;

wherein R ll and R each represents an alkyl group R5 represents+ CH n; n being 0, or an integer of from 1 to 3.

The above mentioned 2,3-dihydro-lH,6H-l,5- benzodiazocine-2-ones are novel and,'so far, have not been reported in the literature. The structure thereof was decided by the results of elemental analysis and various kinds of instrumental analysis such as ultraviolet absorption spectrum, infrared absorption spectrum, NMR spectrum, mass spectrum, etc., which will be further described in the following Examples.

The reaction solvents suitable for the process making use of the photochemical reaction of this invention are alcohols such as methanol, ethanol, propanol, furfuryl alcohol, benzyl alcohol, ethylene glycol, etc., ethers such as diethyl ether, tetrahydrofuran, dioxane, cellosolve diethyl ether, etc., paraffin such as n-hexane, cyclohexane, pentane, etc., mixed paraffin such as petroleum ether, petroleum benzin, ligroin, etc., aromatic hydrocarbon such as benzene, toluene, xylene, etc., and ketones such as acetone, methylethylketone, cyclohexanone, etc., but halogenated hydrocarbons such as carbon tetrachloride, chloroform, etc. are unsuitable since they generate acidic substances such as hydrogen halogenides by irradiation with ultraviolet rays, thereby changing the structure of the product. As for the light source, ultraviolet rays having a wavelength shorter than 400 mp. are required and, usually, a high pressure mercury lamp is employed.

The process of this invention will be further explained by the following several Examples.

EXAMPLE 1 300 mg spiro(indoline-2,5'-isoxazoline-2) is dissolved in 100 of 5-chloro-3'-phenyl-l,3,3-trimethyl- TABLE 2 Value of elemen- Starting material The resulting compound tal analysis C H N C H N Found value (72) 69.49 5.86 8.36 69.43 5.87 8.34 Anal. Calcdv for c,,.H.,,N.,oci (a) 69.59 5.86 8.57 69.59 5.86 24.57 Melting point (C) 167 ii I75 Molecular ion 326.!159 peak (M+) 326 (326.! I85 calculated as w m z IR absorption l555 (W) spectrum (cm U 1560 (W) 1650 (S) NMR spectrum 1.25 (S, 3H) 1.39 (5. 3H) 1.34 (S. 3H) .49 (5, 3H) 2.61 (S. 3H) 3.02 (S, 3H) (ppm) 3.03. 3.33 AB- 3.00. 326 AB- type type 2H 2H 3.38, 3.69 iJ|=l8D 3.39, 3.65 Lli=l5 6 cps cps UV absorption spectrum (mp) nuclear proton 8H nuclear proton SH conversion amount a was determined by the change of the absorbancy index at the wavelength of 261 mp. at which the starting material, 5-chloro-l,3,3-trimethylspiro(indoline-2,5-isoxazoline-2), has its absorption maximum ()t max), according to the following formula. The convertion amount a is given in Table 1.

The ultraviolet absorption spectrum of the product of this reaction denies the indoline skeleton, the infrared absorption spectrum shows the existence of secondary amide and, from the NMR spectrum, which shows the fact that the two adjacent methyl groups are not equivalent and that the hydrogen atoms connected to methylene groups are not equivalent either, it is concluded that the compound is a non-symmetric cyclic compound.

The fragmentation of mass spectrum, the mechanism of production, etc., all support the 8-chloro-2,3- dihydro-2-oxo-4-phenyl-l ,6,6-trimethyl-1H,6H-l ,5- benzodiazocine structure.

The mechanism of the production is assumed as follows; a=e-eo/e eoX lOO Rt R-g l I CHr-C-R wherein 6 IS the absorbancy index at 261 m after t minutes of irradiation, e, is the absorbancy index at 261 O N w my at the time t=0, and e is the absorbancy index at R I 261 m at the time =60. R3

WWW 7, TABLE 1 Irradiation time (min.) 0 o 5 1 2 3 5 2 I0 15 30 40 Conversion amount a o 13 27 35 48 as 87 92 99 100 100 I00 6 2 I 5 beiiiodiazocine) having a melting point of293 4 c.

Ii] Hemmer ed ebsifit'in spectr umrtlie feslfingcompound has the tertiary amide absorption at 1,685 cm, and y N at 1,567 cm. In the mass spectrum, molec- 5 ular ion peak (M+) of 430.2402 was observed.

EXAMPLE 5 200 3 mg bf 3,3 bis[5 -chloro-1,3,3-trimethylspiro(indoline-2,5-isoxazoline-2)] was treated in the same way as is described in Example 4 to yield 140 mg N-C CH2 (70 percent) of 4,4-bis(8-chloro-2,3-dihydro-2-oxo- 1 1 ll l,6,6-trimethyl-1l-I,6H-1,5-benzodiazocine) having a melting point higher than 300C. 7 In the infrared spectrum, the resulting compound has EXAMPLE 2 the tertiary amide absorption at 1685 cm and 7 N 1 300 mg of 5-ethoxycarbonyl-3'-phenyl-1,3,3- at 1575 cm V trimethyl-spiro (indoline-2,5'-isoxazoline-2) was irra- EXAMPLE 6 diated in the same way as is described in Example 1 and I 220 7 I,

. mg of 3 ,3 -b1s[5-ethoxycarbonyl-l,3,3- 2o acted and treated in the same way as is described in :2??? f g f f igi f'gz Example 4 to yield 170 mg 77 percent) of 4,4-bis(8-.

' p ethoxycarbonyl-Z,3-dihydro-2-oxo-l ,6,6-trimethyl- 364.1762 is observed, which is in agreement with the 1H6H4fibenzodiazocinel The resulting Compound calculated value of .364'l786 basgd on C22H2N2O3' 25 has a melting point of 270-1C, has the tertiary amide Therefore, the resulting compound 18 understood to be absorption at 1 685 and y N at 1575 in a photoisomer of l Starting material In ad.dition in the infrared absorption spectrum thereof. The molecuthe infrared absorption spectrum, the absorption of ter- [at ion peak M+ of 574 2775 is observed which is in tiary amide which does not exist in the starting material newly appears at 1673 cm, while the ester absorption at 1714 cm remains.

The pattern of the NMR spectrum is the same as that AMPLE 7 V 7 of the starting material, but each of the chemical shifts V v 7 W V v I V v and bondgo tants are different. The NMR spectrum 400 mg of the high molecular weight compound (reis given in Table 3. duced viscosity: 1; sp/c 0.49) having a main chain of T BLEE v Starting material Photoisomer NMR 1.26 s, 3H) 1.43 s. 3H) 1.40 s. 3H) 1.53 (s, 3H) spectrum 1.24. 1.35. 1.48 (t, 3H) 1.27, 1.39, 1.51 (t, 3H) (ppm) 2.73 (s, 31-1) 3.07 (s, 3H)

3.08 3.39 AB lypc 2H 2.96, 3.21 A8 type 2H 3.45, 3.76 J =l8.6cps 3.36, 3.62 J =l5.3cps

4.16, 4.28. 4.40. 4.52 (q,2HJ 420,432,444, 4.56 (q,2H)

EXAMPLE 3 spiro(indoline-2,5'-isoxazoline-2) as repeating units 300 mg of 1,1,3-trimethyl-3-p-to1yl-spiro(indoline- 5O andwmggliggpmgi 2,5-isoxazoline-2) was irradiated and treated in the onion: CH1 CH3 same way as is described in Example 1 to isolate the f (H isomer 2,3-dihydro-2-oxo-1,6,6-trimethyl-4-p-tolylr lH,6I-l-1,5-benzodiazocine in a quantitative amount. I Q

The resulting compound is recrystallized from cyclohexanone in percent yield, and the melting point L '1 thereof is C. In the infrared spectrum thereof, the Uh m X absorption of a tertiary amide appears at 1660 cm. was dissolved in tetrahydrofuran and was reacted for 2 hours in the same irradiation apparatus as that in the EXAMPLE 4 60 earlier Examples. The reaction solution was then con- 220 mg of 3',3-bis[1,3,3-trimethyl-Sp r0(in olinecentrated under reduced pressure and, the concentrate 2,5 '-isoxazoline-2)] was dissolved in 150 ml of tetrahywas poured into 500 ml of methanol to obtain a precipidrofuran. and was irradiated in the same way as is detate (reduced viscosity: 'nsp/c=0.45). scribed in Example 1, and treated in the same way to The ultraviolet absorption spectrum of the photoisoyield the 210 mg (95 percent) of crude crystal. The re- 65 merization reaction of the higher molecular compound sulting crystal was recrystallized from ethanolin Example 7 is given in FIG. 2. tetrahydrofuran to yield yellowish prismaticcrys tal of The data was observed by exposing said tetrahydro- 4,4" bis(2,3-dfliydro 2 oxo-1 ,6 ,6 trimethyl-1 H, 61-1-1, furan solution of the compound (3.0 g/l) to the light of agreement with the calculated value of 5742791 based the UVL-30OP high pressure mercury lamp made by Rikoo Kagaku Sangyo Co., Ltd. for O, 20, 40, 60, 80

and 100 minutes. The yield was 350 mg. The resulting compound was reprecipitated in a tetrahydrofuran-methanol system,

' and various spectra were observed. In the infrared absorption spectrum of this compound, carbonyl absorption (which does not exist in the starting material) appears at 1,680 cm", which overlaps with the infrared absorption spectrum of 4,4-bis(8-chloro-2,3-dihydro- 2-oxol ,6,6-trimethyl- I I-I,6H-1 ,S-benzodiaz'ocine In the NMR spectrum, the spectrum of the starting material is not observed at all, and the starting compound was almost completely photoisomerized to the high molecular compound having the 2,3-dihydro-2-oxo- I ,6,6-trimethyll H,6I-I-I ,S-benzodiazocine skeleton as repeating units. The NMR spectrum is given in Table The resulting high molecular weight compound can be formulated into film, and strong film was obtained by coating an organic solution of the polymer,

T'KBIIEW wherein said organic solution is cyclohexane, methanol tetrahydrofuran.

3. A process for preparing 2,3-dihydro-l H,6H-l,5 benzodiazocine-Z-on derivatives as claimed in claim I wherein said formula (I) is the compound of the formula (III), and formula (II) is the compound of the formula (IV).

Starling high molecular compound Photoisomcrizcd high molecular compound By a differential thermal analysis an, absorption pealc was observed at 244C. This pattern is similar to that of the starting high molecular weight compound.

What is claimed is: g

l. A process for preparing 2,3-dihydro-lH,,6I-I-l,5- benzodiazocine-Z-one derivatives represented by the formula (II), comprising irradiating an organic solution of spiro(indoline-2,5-isoxazoline-2) represented by the formula( I) with light 1.3, 1.2 broad doublet, 6H 1.4, broad singlet, 6H

NMR spectrum 2,7 broad singlet, 3H 3.0, broad singlet, 3H

3.4 broad singlet, 4H 3.6, broad singlet, 2H

4.0 broad singlet, 2H 4.0, broadsinglet, 4H

6.3-73 multiplet, 6H 7.], broad singlet, 6H

wherein R R and R are a hydrogen atom or alkyl group having l-4 carbon atoms, R, and R are a hydrogen atom, alkyl group having 1-4 carbon atoms, alkoxycarbonyl group having 1-4 carbon atoms, nitro group or a halogen atom.

4. A process for preparing 2,3-dihydro-ll-I,6H-l,5- benzodiazocine-2-on derivatives as claimed in claim 3 wherein said formula (III) is the compound of the formula (a), and formula (IV) is the compound of the formula (b) CH: CH;

5. A process for preparing 2,3-dihydro-1H,6H-l,5- benzodiazocine-Z-on derivatives as claimed in claim 3 wherein said formula (III) is the compound of the formula (c), and formula (IV) is the compound of the formula (d) CH3 CH3 1, H l Ha 6. A process for preparing 2,3-dihydro-lH,6I-I-l,5- benzodiazocine-2-on derivatives as claimed in claim 3 wherein said formula (III) is thecompound of the formula (e), and formula (IV) is the compound of the formula (f) 7. A process for preparing 2,3-dihydro-lI-I,6I-I-1,5- benzodiazocine-Z-on derivatives as claimed in claim 3 wherein said formula (III) is the compound of the formula (g), and formula (IV) is the compound of the for mula (h) CzHs HSC

8. A process for preparing 2,3-dihydro-lI-I,6H-l,5- benzodiazocine-Z-on derivatives as claimed in claim 1 wherein said formula (I) is the compound of the formula (V), and formula (II) is the compound of the formula (VI) wherein R,, R andR are a hydrogen atom or alkyl group having l-4 carbon atoms, R, and R are a hydrogen atom, alkyl group having 1-4 carbon atoms, kqt ses o x srwpthav If! c b nwi group or a halogen atom, R represents direct bond, CH or n being 0,1, 2 or 3.

9. A process for preparing 2,3-dihydro-lI-I,6H-1,5 benzodiazocine-Z-on derivatives as claimed in claim 8 wherein said formula (V) is the compound of the formula (i), and formula (VI) is the compound of the formula (j) I HaC 0 CH:

10. A process for preparing 2,3-dihydro-lH,6H-l ,5- benzodiazocine-2-on derivatives as claimed in claim 8 wherein said formula (V) is the compound of the formula (k), and formula (VI) is the compound of the formula (l) riff) 11. A process for preparing 2,3-dihydro-lH,6H-l,5- bezodia'zocine-Z-on derivatives as claimed in claim 8 wherein said formula (V) is the compound of the formula (m), and formula (VI) is the compound of the cgmooo Hac CH3 i T 00011.0, '"T f cnnoco 113C 0 O Ulla 12. A process for preparing 2,3-dihydro-lH,6I-I-1,5- benzodiazocine-Z-on derivatives as claimed in claim 8 wherein said formula (V) is the compound of the formula (o), and formula (VI) is the compound of the for mula (p) 13. A process for preparing 2,3vdihydro-lI-I,6I-I-l,5- benzodiazocine-2-on derivatives as claimed in claim 1 wherein said formula (I) is the compound of the formula (VII), and formula (II) is the compound of the formula (VIII).

' fj Ci LOX R: R3 X vvherein R R and R each represents a hydrogen atom or alkyl group having 1-4 carbon atoms; R represents R represents CH n being 0 or an integer of l to 3; X represents degree of polymerization.

14. A process for preparing 2,3-dihydro-1I-I,6I-l-l,5- benzodiazocine-2-on derivatives as claimed in claim 13 wherein said formula (VII) is the compound of the formula (q), and formula (VIII) is the compound of the formula (r).

Ha C

l IIaC O CH; X

wherein X represents the degree of polymerization.

15. A process for preparing 2,3-dihydro-iI-I,6H-l ,5- benzodiazocine-Z-on derivatives as claimed in claim 13 wherein said formula (VII) is the compound of the formula (s), and formula (VIII) is the compound of the formula (t) wherein X represents the degree of polymerization. 

2. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 1 wherein said organic solution is cyclohexane, methanol tetrahydrofuran.
 3. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 1 wherein said formula (I) is the compound of the formula (III), and formula (II) is the compound of the formula (IV).
 4. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 3 wherein said formula (III) is the compound of the formula (a), and formula (IV) is the compound of the formula (b)
 5. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 3 wherein said formula (III) is the compound of the formula (c), and formula (IV) is the compound of the formula (d)
 6. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 3 wherein said formula (III) is the compound of the formula (e), and formula (IV) is the compound of the formula (f)
 7. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 3 wherein said formula (III) is the compound of the formula (g), and formula (IV) is the compound of the formula (h)
 8. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 1 wherein said formula (I) is the compound of the formula (V), and formula (II) is the compound of the formula (VI)
 9. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 8 wherein said formula (V) is the compound of the formula (i), and formula (VI) is the compound of the formula (j)
 10. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 8 wherein said formula (V) is the compound of the formula (k), and formula (VI) is the compound of the formula (l)
 11. A process for preparing 2,3-dihydro-1H,6H-1,5-bezodiazocine-2-on derivatives as claimed in claim 8 wherein said formula (V) is the compound of the formula (m), and formula (VI) is the compound of the formula (n)
 12. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 8 wherein said formula (V) is the compound of the formula (o), and formula (VI) is the compound of the formula (p)
 13. A process foR preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 1 wherein said formula (I) is the compound of the formula (VII), and formula (II) is the compound of the formula (VIII).
 14. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 13 wherein said formula (VII) is the compound of the formula (q), and formula (VIII) is the compound of the formula (r).
 15. A process for preparing 2,3-dihydro-1H,6H-1,5-benzodiazocine-2-on derivatives as claimed in claim 13 wherein said formula (VII) is the compound of the formula (s), and formula (VIII) is the compound of the formula (t). 